Process for the preparation of low mooney nitrile terpolymers

Abstract

The present invention relates to a process for the production of optionally hydrogenated nitrile terpolymers having lower molecular weights, lower Mooney viscosities and narrower molecular weight distributions than those known in the art. The present invention also relates to optionally hydrogenated nitrile terpolymers having lower molecular weights, lower Mooney viscosities and narrower molecular weight distributions than those known in the art.

1 . A process for preparing nitrile terpolymers comprising at least one conjugated diene, at least one α,β-unsaturated nitrile and at least one monomer selected from the group consisting of alkyl esters of unsaturated carboxylic acids, alkoxyalkyl acrylates and ethylenically unsaturated monomers other than dienes, the process comprising: 
 reacting the nitrile terpolymer in the presence of at least one compound selected from the group consisting of compounds of the general formulae I, II, III, IV, or V;                          wherein:    M is Os or Ru,    R and R 1  are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 1 -C 20  alkyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl,    X and X 1  are independently any anionic ligand, and    L and L 1  are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidinylidenes or any neutral carbine, optionally, L and L 1  can be linked to one another to from a bidentate neutral ligand;                          wherein:    M 1  is Os or Ru;    R 2  and R 3  are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 1 -C 20  alkyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl,    X 2  is a anionic ligand, and    L 2  is a neutral π-bonded ligand, independent of whether they are mono- or polycyclic,    L 3  is a ligand selected from the group consisting of phosphines, sulfonated phosphines, fluorinated phosphines, functionalized phosphines bearing up to three aminoalkyl-, ammoniumalkyl-, alkoxyalkyl-, alkoxylcarbonylalkyl-, hydrocycarbonylalkyl-, hydroxyalkyl- or ketoalkyl- groups, phosphites, phosphinites, phosphonites, phosphine amines, arsines, stibenes, ethers, amines, amides, imines, sulfoxides, thioethers and pyridines,    Y is a non-coordinating anion,    n is an integer in the range of from 0 to 5;                          wherein    M 2  is Mo or W,    R 4  and R 5  are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 1 -C 20  alkyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C2-C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl,    R 6  and R 7  are independently selected from any unsubstituted or halo-substituted alkyl, aryl, aralkyl groups or silicon-containing analogs thereof,                          wherein:    M is Os or Ru,    R and R 1  are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted alkyl,    X and X 1  are independently any anionic ligand, and    L and L 1  are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidinylidenes or any neutral carbine, optionally, L and L 1  can be linked to one another to from a bidentate neutral ligand;                          wherein:    M 1  is Os or Ru;    R is hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 1 -C 20  alkyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl;    X is selected from any anionic ligand; and    L 1  is a neutral π-bonded ligand, preferably but not limited to arene, substituted arene, heteroarene, independent of whether they are mono- or polycyclic;    L is a ligand selected from the group consisting of phosphines, sulfonated phosphines, fluorinated phosphines, functionalized phosphines bearing up to three aminoalkyl-, ammoniumalkyl-, alkoxyalkyl-, alkoxylcarbonylalkyl-, hydrocycarbonylalkyl-, hydroxyalkyl- or ketoalkyl- groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines, stibenes, ethers, amines, amides, imines, sulfoxides, thioethers and pyridines;    Y is a non-coordinating anion.    
   
   
       2 . A process for preparing low molecular weight hydrogenated nitrile terpolymers comprising hydrogenating the reaction product of  claim 1 .  
   
   
       3 . The process according to  claim 1 , wherein in the compounds of formula I, L and L′ are trialkylphosphines, X and X′ are chloride ions and M is ruthenium.  
   
   
       4 . The process according to  claim 1 , wherein the compounds of formula V, L is trialkylphosphine, L′ is methyl-4-iso-propylphenyl, X is a chloride ion, R is phenyl and M is ruthenium.  
   
   
       5 . The process according to  claim 1 , wherein the compound is [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidiniylidene]dichloro(phenylmethylene)(tricyclohexylphosphine).  
   
   
       6 . The process according to  claim 1 , further comprising the presence of a co-olefin.  
   
   
       7 . The process according to  claim 6 , wherein the co-olefin is a C 2  to C 16  linear or branched olefin.  
   
   
       8 . The process according to  claim 7 , wherein the olefin is ethylene, isobutene, styrene or hexene.  
   
   
       9 . The process according to  claim 1 , further comprising the presence of a solvent.  
   
   
       10 . The process according to  claim 2 , wherein the hydrogenation is conducted in the presence of a hydrogenation catalyst.  
   
   
       11 . The process according to  claim 10 , wherein the catalyst is of the formula  
       (R 8   m B) 1 RhX 3   n    
     wherein 
 R 8  is a C 1 -C 8 -alkyl group, a C 4 -C 8 -cycloalkyl group a C 6 -C 15 -aryl group or a C 7 -C 15 -aralkyl group, B is phosphorus, arsenic, sulfur, or a sulphoxide group S=0, X 3  is hydrogen or an anion.  
 
   
   
       12 . The process according to  claim 11 , wherein the catalyst is selected from the group consisting of tris-(triphenylphosphine)-rhodium(I)-chloride, tris(triphenylphosphine)-rhodium(III)-chloride and tris-(dimethylsulphoxide)-rhodium(III)-chloride, and tetrakis- (triphenylphosphine)-rhodium hydride of formula ((C 6 H 5 ) 3 P) 4 RhH, and the corresponding compounds in which triphenylphosphine moieties are replaced by tricyclohexyl-phosphine moieties.  
   
   
       13 . The process according to  claim 10 , further comprising the presence of a co-catalyst, preferably in the presence of triphenylphosphine.  
   
   
       14 . A nitrile terpolymer prepared according to  claim 1 .  
   
   
       15 . A hydrogenated terpolymer prepared according to  claim 2 , wherein the hydrogenated terpolymer has a Mooney viscosity (ML(1+4)@ 100° C.) of between 1-55.  
   
   
       16 . A hydrogenated terpolymer according to  claim 15 , wherein the hydrogenated terpolymer has a Mooney Viscosity (ML(1+4)@ 100° C.) of between 5-50.  
   
   
       17 . A hydrogenated terpolymer according to  claim 16 , wherein the hydrogenated terpolymer has a Mooney Viscosity (ML(1+4)@ 100° C.) of between 10-45.  
   
   
       18 . A hydrogenated terpolymer according to  claim 17 , wherein the hydrogenated terpolymer has a Mooney Viscosity (ML(1+4)@ 100° C.) of between 15-40.  
   
   
       19 . The nitrile terpolymer according to  claim 14 , wherein the nitrile terpolymer has a Mooney viscosity (ML(1+4)@ 100° C.) of below 25.  
   
   
       20 . The nitrile terpolymer according to  claim 14 , wherein the nitrile terpolymer has a Mooney viscosity (ML(1+4)@ 100° C.) of below 20.  
   
   
       21 . The nitrile terpolymer according to  claim 14 , wherein the nitrile terpolymer has a Mooney viscosity (ML(1+4)@ 100° C.) of below 15.  
   
   
       22 . The nitrile terpolymer according to  claim 14 , wherein the nitrile terpolymer has a Mooney viscosity (ML(1+4)@ 100° C.) of below 10.  
   
   
       23 . The process according to  claim 13 , further comprising the presence of a proton acceptor that is non-coordinating with a metal complex catalyst.  
   
   
       24 . The process according to  claim 23 , wherein the proton acceptor is epoxidized soy bean oil.